Sodium Cyanide → Isopropyl 4-cyano-5-ethylthiophene-2-carboxylate

HRID 2298637ノート

反応式

HRID 2298637 の反応式
Br[C:2]1[CH:3]=[C:4]([C:9]([O:11][CH:12]([CH3:14])[CH3:13])=[O:10])[S:5][C:6]=1[CH2:7][CH3:8].[Cu](C#N)[C:16]#[N:17].[C-]#N.[Na+]>CN(C)C=O>[CH2:7]([C:6]1[S:5][C:4]([C:9]([O:11][CH:12]([CH3:14])[CH3:13])=[O:10])=[CH:3][C:2]=1[C:16]#[N:17])[CH3:8]

参加物

5

反応物 3

HCID 8929Sodium CyanideHCID 18536986Isopropyl 4-bromo-5-ethylthiophene-2-carboxylateHCID 178418260HCID 178418260、化合物

生成物 1

HCID 18537065Isopropyl 4-cyano-5-ethylthiophene-2-carboxylate収率 53%

試薬・触媒・溶媒 1

HCID 6228Dimethylformamide溶媒

実験手順

A stirred solution of 4 g (14.4 mmol) of isopropyl 4-bromo-5-ethylthiophene-2-carboxylate was refluxed in dry dimethylformamide (50 mL) with copper cyanide (1.94 g, 22 mmol) for 8 hours. The cooled mixture was poured into 0.1 M sodium cyanide (500 mL) and extracted with diethyl ether (4×50 mL). The organic layers were washed twice with brine (50 mL) and dried over anhydrous sodium sulfate. The solvents were removed in vacuo. Column chromatography on silica gel (400 g), eluting with hexanes:ethyl acetate 9/1 (v:v) gave isopropyl 2-ethyl-3-cyano-thiophene-5-carboxylate (1.7 g, 53%) as a pale yellow oil. 1H-NMR (DMSO-d6; 300 MHz) δ8.03 (s, 1H), 5.10 (septet, 1H, J=6.2 Hz), 3.04 (q, 2H, J=7.5 Hz), 1.31 (t, 3H, J=7.5 Hz), 1.30 (d, 6H, J=6.2 Hz). Mass spectrum (ESI m/z): Calcd. for C11H13NO2S 224.1 (M+H), found 224.0.

後処理

  1. extractionextracted with diethyl ether (4×50 mL)
  2. washThe organic layers were washed twice with brine (50 mL)
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvents were removed in vacuo
  5. washColumn chromatography on silica gel (400 g), eluting with hexanes

出典と根拠

ORDレコード
ord-5893591dae844259955b8563adcc4d92
出典データセット
uspto-grants-2002_12
特許番号
US06492403B1

反応ノート

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